Process of making nitro-amino derivatives of the anthraquinone series.



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UNITED s'rATEs PATENT 7 OFFICE;

ARTHUR ZITSCHER AND ERNST JULIU BATH, OF OFFENBACH-ON-THE-MAIN,

GERMANY, ASSIGNOBS TO CORPORATION OF 'CHEMISCIEUE FABRIK GREISHEIM-ELEKTRON, OF FRANKFOBT-ON-THE-MAIN, GERMANY.

PROCESS OF MAKING NITRO-AMINO DERIVATIVEQ OF THE ANTHRAQUINONE SERIES.

T0 alt whom it may concern:

Be it known that we, ARTHUR Zirsonan and ERNST JULIUS RATH,bothchemists, doctors of philosophy, and'cit'izens'of the German Empire, andresidents of Ofi'enbach-on-the- Main, in the Grand Duchy of'Hesse, Germany, with post-office addresses Friedrichstrasse- 31 and Kaiserst-rasse115 respectively, have invented new and useful Improvements in theProcess of Making Nitro- Amino Derivatives of the Anthraquinone Series,of. which the following is a specification.

According to this invention, the nitramins of the anthraquinone seriescan be-converted in absenceof nitratable substances such as phcnol.inthe nitro-amino derivatives by mineral acids, except concentrated nitricacid. Thus the anthraquinone-anitramin, which is described in the Ger-'man specification No. 156803, yields by treatment with concentratedsulfuric acid a mixture of 1 amino 2' nitro anthraquinone and 1-amino-4-nitroanthraquinone, whereas the anthraquinone-(l-nitraminyields almost exclusively 1-nitr0-2.-'amin0ant hra-' qninone. Analogousproducts are obtained from 1:5-dinitramin and 2:6-dinitraminofanthraquinone or from the substitution products of the vnitramins.

The anthraquinoneB-nitramins can be made by heating thecorrespondingisodiazo compounds with oxidizing agents, for example with sodiumhypochlorite or potassium fcrricyanid. i

The simplest representative of the anthraquinone-[-nitramins hasprobablyhthe The nitro amino derivatives "of anthraquinone can be easilytransformed into the corresponding diamino-derivatives of anthraquinoneby reduction, for example-with sodium sulfid. i

In carrying out the new process practiformula:

Specification of Lctters'latent.

Patented July 8,1913.

Application filed November 30, 1912. Serial No. 734,237.

cally we can proceed-as being by weight: 7

Exa i npl e I: 1.0 parts'of' anthraquinone-anitramin described in theGerman specification No. 156803, are introduced into 100 parts of coldconcentrated sulfuric acid and the mixture is stirred for an hour atordinary temperature, and then the solution is poured, onto ice. Themixture of 1:2- and 1:4: amino nitro anthraquinone thus ob tained in theform of a red precipitate, is filtered off, washed with water, untilitshows follows, the parts neutral reaction and dried. The same result isobtained by heating anthraquinonea-nitramin with concentratedhydrochloric acid or phosphoric acid. i

Example II: 10 parts of anthraquinone-finitramin obtained bytreating theli-iso-diazotate of anthraquinon'e with sodium hypochlorite areintroduced into 100 parts of" concentrated sulfuric acid; after stirringfor an hour the solution is poured onto ice and the productofconversion, which has separated in the form of a dark yellow prevcipitate, is filtered, washed with water, until it shows neutralreaction, and dried. The

body, thus'obtained, corresponds in its properties withl-nitro-2-amino-anthraqumone' (see Dissertation,

described by Torres Braunschweig 1910, page 13). Bytreatment withreducing agents it is transformed into the well known 1:2-diamino-anthraquinone, which melts at 242244 C. i

Now what we claim and desire to secure by Letters Patent is thefollowing:

The process of makingnitrmamino derit- 'atives of the anthraquinoneseries consisting in treating the nit-ramins of anthraquinone withnon-nitrating mineral acids in absence of nitra-table substances. 1

In testimony, that we claim the foregoing as our invention, we havesigned our names in presence of two witnesses, thisfourteentli day ofNovember 1912. V

V ARTHUR ZITSCHER.

ERNST JULIUS RATH. W'itnesses:

PETER LAUrsNscHLIA'cER, FRITZ Dr'zsoiz.

